Living olefin polymerization processes

ABSTRACT

Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

This application is a continuation of Ser. No. 08/843,161 filed Apr. 11,1997 U.S. Pat. No. 5,889,128.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to living olefin polymerizationprocesses, and more specifically to initiators for such processes thatare stable under reaction conditions in the absence of olefin monomersuch that polymers of low polydispersity can be synthesized.

2. Discussion of the Related Art

Polymers are used in a large number of applications, and a great deal ofattention has been paid to developing synthetic routes that result inpolymers having optimal physical and chemical properties for a givenapplication.

Block copolymers are one class of polymers that have broad utility. Forexample, block copolymers have been employed as melt processablerubbers, impact resistant thermoplastics and emulsifiers. As a result,these materials have been the focus of a particularly large amount ofresearch and development both in industry and academia, and a variety ofapproaches to block copolymer synthesis have been developed.

When preparing a block copolymer, it is generally desirable to use asynthetic technique that allows for control over the chain length ofeach polymer block and the polydispersity of the resulting blockcopolymer. For some time, attempts to provide such a method have focusedon block copolymer formation by living polymer synthesis. In livingpolymer synthesis, a metal-containing initiator having either ametal-carbon bond or a metal-hydrogen bond is reacted with an olefinmonomer to form a polymer chain via the successive insertion of thefirst olefin monomer into a metal-carbon bond between the metal of theinitiator and the growing polymer chain. If the initiator is ametal-hydride complex, the first metal-carbon bond is formed when theolefin inserts into the metal-hydride bond. When the olefin monomer isdepleted, a second olefin monomer is added, and a second polymer blockis formed by successively inserting, into the metal-carbon end group,the second monomer, ultimately resulting in a block copolymer includinga first polymer block connected to a second polymer block. Since eachpolymer block is formed sequentially, the initiator and propagatingspecies should be stable under reaction conditions in the absence ofolefin monomer.

To provide a block copolymer having sizable polymer blocks of lowpolydispersity, the rate of chain propagation (i.e., olefin monomerinsertion into the metal-carbon bond) should be substantially greaterthan the rate of chain termination or transfer. To prepare a blockcopolymer having the lowest possible polydispersity, the rate ofinitiation should be at least as great as the rate of propagation.

Polymerization termination is typically dominated by β-hydrideelimination with the products being a polymer chain having a terminalcarbon-carbon double bond and the initiator having a metal-hydrogenbond. Termination of polymerization also can occur if the initiatordecomposes in some other manner, such as transfer of the polymer chainfrom the initiator to some other element that is relatively inactive inor for olefin polymerization. Hence, the achievable chain length ofcopolymer blocks and the polydispersity of the block copolymer areprincipally determined by the relative rates of olefin insertion andβ-hydride elimination, as well as initiator stability toward other modesof decomposition, especially in the absence of olefin monomer.

Attempts at synthesizing polymers using living polymer synthesis haveemployed a variety of initiators. For example, as reported in JACS 118,10008 (1996), McConville and co-workers have used a diamido-titaniuminitiator to form polymers by polymerizing α-olefins. In addition,Turner and co-workers have developed a hafnium-containingcyclopentadienyl initiator for preparing block copolymers from α-olefinmonomers (published PCT patent application WO 91/12285). Furthermore,Horton and co-workers report diamido-group IVB metal initiator effectivein providing homopolymer synthesis (Organometallics 15, 2672 (1996)).

Despite the commercial motivation for developing a living polymersynthetic method for block copolymer preparation, known methods of blockcopolymer synthesis can suffer from a variety of problems. For example,the initiators used can be unstable under reaction conditions in theabsence of olefin monomer, resulting in an inability to form additionalhomopolymer blocks to form a block copolymer. Moreover, the efficiencyof block copolymer formation can be reduced due to the formation ofsignificant amounts of homopolymer. In addition, due to the lowtemperatures used, the products formed using many known initiators haverelatively low molecular weights and are more appropriately classifiedas oligomers.

As seen from the foregoing discussion, it remains a challenge in the artto provide a method of synthesizing block copolymers that includes theuse of a initiator that is stable in the absence of olefin monomer suchthat the resulting block copolymers have low polydispersities. Such aninitiator would also offer the advantage of resulting in relativelysmall amounts of homopolymer synthesis.

SUMMARY OF THE INVENTION

In one illustrative embodiment, the present invention provides acomposition of matter having a structure:

[R₁—X—A—Z—R₂]²⁻

X and Z are each group 15 atoms. R₁ and R₂ are each a hydrogen atom orgroup 14 atom-containing species. A is either

L₁—Y₁—L₂

or

Y₁ is a group 16 atom, and Y₂ is a group 15 atom. R₃ is H or a group 14atom-containing species. L₁ and L₂ are each dative interconnectionsincluding at least one group 14 atom bonded to Y₁ or Y₂.

In another illustrative embodiment, the present invention provides amethod of synthesizing a block copolymer. The method comprisesperforming a first reaction and a second reaction. In the firstreaction, a first monomeric species containing a terminal carbon-carbondouble bond is exposed to an initiator containing a metal, and theterminal carbon-carbon double bonds of the first monomeric species areallowed to insert successively into the initiator to form a carbon-metalbond thereby forming a first homopolymeric block of the first monomericspecies connected to the metal of the initiator. In the second reaction,a second monomeric species containing a terminal carbon-carbon doublebond is exposed to the initiator, and terminal carbon-carbon doublebonds of the second monomeric species are allowed to insert successivelyinto the initiator, first inserting into the bond between the block ofthe first homopolymeric block and the metal of the initiator, therebyforming a copolymer including the first homopolymeric block connected toa homopolymeric block of the second monomeric species, the copolymerhaving a polydispersity of no more than about 1.4.

In yet another illustrative embodiment, the present invention provides amethod of synthesizing a block copolymer. The method comprises: exposinga first monomeric species having a terminal carbon-carbon double bond toan initiator including a metal and allowing terminal carbon-carbondouble bonds of the first species to insert successively into theinitiator to form a metal-carbon bond thereby forming a firsthomopolymeric block of the first monomeric species having a bond to themetal of the initiator; and exposing a second monomeric speciescontaining a terminal carbon-carbon double bond to the initiator andallowing terminal carbon-carbon double bonds of the second species toinsert successively into the initiator, first inserting into the bondbetween the first homopolymeric block and the metal, thereby forming acopolymer including the first homopolymeric block connected to a secondhomopolymeric block of the second monomeric species, the methodproducing no more than about 25% by weight of the first homopolymer orthe second homopolymer relative to a total amount of polymer product.

In a further illustrative embodiment, the present invention provides ablock copolymer which comprises a first homopolymer block and a secondhomopolymer block connected to the first homopolymer block. The firsthomopolymer block comprises a polymerization product of at least aboutten units of a first monomeric species having a formula H₂C═CHR₁. Thesecond homopolymer block comprises a polymerization product of at leastabout ten units of a second, different monomeric species having aformula H₂C═CHR₂. R₁ and R₂ can be the same or different, and each are Hor a linear, branched, or cyclic hydrocarbon that is free of non-carbonheteroatoms. The block copolymer has a polydispersity of at most about1.4.

In still a further illustrative embodiment, the present inventionprovides a method of polymerization. The method comprises: reacting aninitiator having a metal atom with a monomeric species having a terminalcarbon-carbon double bond to allow terminal carbon-carbon double bondsof monomers to insert successively into the initiator to form ametal-capped polymer of the monomeric species connected to the metalthrough a metal-carbon bond. The metal-capped polymer is stable, in asolvent essentially free of the monomeric species and electron donorssuch as water and free oxygen at a temperature of at least about −50° C.The metal-capped polymer is capable of then reacting further withmonomeric species and inserting the monomeric species successively intoa metal carbon bond.

DETAILED DESCRIPTION

In one aspect, the present invention relates to a ligand (referred toherein as [LIG]) having the following representative structures:

X and Z are group 15 atoms such as nitrogen and phosphorous that areeach selected to form an anionic or covalent bond with a metal atom,particularly a transition metal, while simultaneously including twosubstituents (e.g., L₁ and R₁ or L₂ and R₂). Y₁ is a group 16 atom suchas oxygen or sulfur that is selected to form a dative bond with anotheratom such as a metal atom, particularly a transition metal, whilesimultaneously including two substituents (e.g., L₁ and L₂). Y₂ is agroup 15 atom such as nitrogen or phosphorus that is selected to form adative bond with another atom such as a metal atom, particularly atransition metal, while simultaneously including three substituents(e.g., L₁, L₂ and R₃). represents a dative interconnection between X andZ, such as one or more group 14 atoms. In certain embodiments, Y₁ ispreferably oxygen and X and Z are the same atom, more preferably, X andZ are each nitrogen atoms.

A “dative bond” herein refers to a bond between a neutral atom of aligand and a metal atom in which the neutral atom of the ligand donatesan electron pair to the metal atom. As used herein, an “anionic bond”denotes a bond between a negatively charged atom of a liaand and a metalatom in which the negatively charged atom of the ligand donates anelectron pair to the metal atom.

L₁ and L₂ each represent a dative interconnection between X, Y₁, Y₂and/or Z. L₁ and L₂ each correspond to at least one atom, preferably 1-4atoms, and most preferably 2 atoms. The atoms that make up theinterconnection most commonly are group 14 atoms, such as carbon orsilicon. Preferably, L₁ and L₂ each represent a C₂ unit such as—(CH₂)₂—, —(CF₂)₂—, —(o-C₆H₄)—, —CH₂Si(CH₃)₂— and the like. In certainembodiments, L₁ and L₂ may be selected such that X, Y₁,Y₂ and/or Z arenot rigidly interconnected (i.e., there is at least one rotationaldegree of freedom between these atoms).

Although depicted in an arrangement in which X is interconnected to Y₁or Y₂ and Y₁ or Y₂ is interconnected to Z, other arrangements of X, Y₁or Y₂ and Z are envisioned to be within the scope of the presentinvention. For example, in certain embodiments, X may be interconnectedto Z through L₁ or L₂. The arrangement of X, Y₁ or Y₂ and Z is limitedonly in that, simultaneously, X and Z should each be selected to formanionic or covalent bonds with a metal atom such as a transition metalwhile Y₁ or Y₂ should each be selected to form a dative bond with ametal atom such as a transition metal. Upon reading this disclosure,those of ordinary skill in the art will recognize a combination of atomsX, Y₁, Y₂ and Z, and interconnections L₁ and L₂ that will provide thiscapability.

R₁-R₃ can be the same or different and preferably are H or group 14species such as linear, branched, cyclic and/or aromatic hydrocarbonsfree of non-group 14 heteroatoms that could bind to an activated metalcenter. One set of exemplary R₁-R₃ units include saturated orunsaturated straight, branched or cyclic hydrocarbons. Another exampleof R₁-R₃ units is trimethylsilyl groups. Still a further example ofR₁-R₃ units is 2,6-disubstituted phenyl rings such as2,6-dimethylphenyl.

In another aspect, the invention relates to metal-containing catalystprecursors, preferably group 4 metal-containing catalyst precursors, foruse in the living polymerization of olefin monomers having terminalcarbon-carbon double bonds. These catalyst precursors are particularlystable under reaction conditions in the absence of such olefin monomer.That is, when the reaction mixture is substantially depleted of theolefin monomer, the catalyst precursor remains stable in the absence ofwater, oxygen, basic donor ligands and the like. As a result of thecatalyst precursor's stability, the resulting polymers (e.g.,homopolymers, random copolymers and/or block copolymers) have lowpolydispersities. Furthermore, when used to prepare block copolymers,the amount of homopolymer produced is relatively low.

Substantial depletion of an olefin monomer relates to a situation inwhich the olefin monomer is present in an amount below the detectionlimit of standard NMR spectrometers such that the olefin monomer cannotbe detected using such standard NMR spectrometers. Typically, an olefinmonomer is substantially depleted when less than about 5% of the olefinmonomer remains as olefin monomer in solution relative to the amount ofolefin monomer initially present in the solution.

The catalyst precursors of the present invention have the followingrepresentative molecular structures:

[R₁—X—L₁—Y₁—L₂—Z—R₂]MR₄R₅ [X—L₁—Y₁—L₂—Z]MR₄R₅

That is,:

M is a metal atom that can form a metal-carbon bond into which an olefincan be inserted. Those of ordinary skill in the art will recognizemetals that meet this requirement. For example, M may be selected frommetals of groups 3-6, late transition metals such as those of group 10,actinides and lanthanides. In one set of preferred embodiments, M isselected from Ti, Zr or Hf. X and Z each form an anionic or covalentbond to M while Y₁ or Y₂ each form dative bonds to M. Preferably, thelength of the M—Y₁ and M—Y₂ bonds is at most about 2.5 Angstroms, morepreferably at most about 2.3 Angstroms, most preferably at most about2.1 Angstroms, depending upon the size of M.

R₄ and R₅ should be good leaving groups such that living polymerizationcan occur via the removal of R₄ or R₅ and the formation of an initiator,as described below. Typically, R₄ and R₅ are substantially similar toR₁-R₃. Preferably, R₄ and R₅ are linear or branched alkyls having alength of from 1-10 carbon atoms. In some embodiments R₄ and/or R₅ canbe hydrogen.

The present invention is not limited by the particular geometricalconfiguration of the catalyst precursor. However, in certainembodiments, the catalyst precursor may have a nonplanar geometry, suchas, for example, trigonal bipyramidal. In some embodiments, it ispreferable that the catalyst precursor have a geometrical configurationsuch that X, Y₁ or Y₂ and Z are interconnected in the same plane.

In a particularly preferred set of embodiments, a catalyst precursor isprovided having one of the structures:

It is to be noted that, in certain embodiments, any or all of theisopropyl groups of [(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]M(R₄)(R₅) may be replacedwith H or branched or straight chain alkyl groups. As will beappreciated by one skilled in the art, such alkyl groups should beselected such that an olefin monomer's access to M during polymerization(described below) is not sterically hindered by these alkyl groups.Typically, such alkyl groups have at most about 20 carbon atoms andinclude, for example, methyl, propyl, t-butyl and the like.

The catalyst precursors can be prepared using standard alkylationtechniques. For example, the protanated ligand (H₂[LIG]) can be reactedwith M(NMe₂)₄ to form [LIG]M(NMe₂)₂ which is then reacted with TMSCl toform [LIG]MCl₂. The [LIG]MCl₂ is reacted with R-MgX to provide [LIG]MR₂.The appropriate reaction conditions of from about −78° C. to about 0° C.in a solvent such as ether, diethyl ether, hydrocarbons, free of oxygenand water, can be selected by those of skill in the art. Alternatively,[LIG]MCl₂ can be reacted with aluminoxane which first reacts to form thedimethyl compound [LIG]M(Me)₂ in situ, and then removes one Me group tomake the active cation, serving as its counterion. This reaction isknown, as described in, for example, published PCT patent application WO92/12162.

During living polymerization, the catalyst precursor is activated viathe removal either R₄ or R₅, typically in situ, to form an initiatorwhich is cationic in nature. Where a stable salt can be synthesized,this salt can be provided, stored, and used directly. Counterions forthe initiator should be weakly-coordinating anions, for example[B(C₆F₅)₄]⁻. Those of ordinary skill in the art can select suitablecounter ions.

The initiator can be reacted with monomeric olefins having a terminalcarbon-carbon double bond (H₂C═CHR₆) to provide polymers, where R₆ ishydrogen or a hydrocarbon such that the olefin can be a straight,branched, cyclic or aromatic hydrocarbon. Furthermore, the hydrocarbonsmay include additional carbon-carbon double bonds. Preferably, anyadditional carbon-carbon double bonds are internal (non-terminal).Preferably, these monomers are substantially devoid of any heteroatoms.Examples of such monomers include, but are not limited to, α-olefinssuch as ethylene, 1-propylene, 1-butene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 4-methyl-1-pentene and the like.

Initiation of the polymerization reaction occurs by insertion of thecarbon-carbon double bond of the species H₂C═CHR₆ into a metal-carbonbond of the initiator. During reaction of the initiator and monomericolefm, chain growth of the polymer occurs by successive insertion of themonomer into a bond formed between the terminal carbon atom of thepolymer chain and the metal atom of the initiator. It is an advantageousfeature of the present invention that, under reaction conditions in theabsence of monomer (described above), such a metal-carbon bond remainsstable for periods of time sufficient to allow depletion of monomer andsubsequent addition of monomer and continued chain growth. For example,the system allows depletion of one monomer H₂C═CHR₆, and addition to thesystem of a additional monomer H₂C═CHR₇ that can be the same monomer(for continued homopolymer growth) or a different monomer (for blockcopolymer synthesis). Preferably, a metal-carbon bond of the initiator,such as a bond between the metal and a polymer chain, remains stable forgreater than about a half an hour at room temperature under reactionconditions in the absence of olefm monomer, water, oxygen, basic donorligands or the like. For most known initiators used in polymerizingthese monomers, the metal-carbon bond formed between the initiator andthe polymer chain is not stable enough for standard analyticaltechniques, such as NMR, to verify the existence of the initiator,indicating that the initiator-polymer chain species is not stable formore than at most about one second at room temperature. In contrast, theinitiating and propagating species of the present invention have beenverified by NMR.

This enhanced stability of this metal-carbon bond is desirable becauseblocks of polymer may be formed in a sequential fashion by adding olefinmonomer, allowing the olefin monomer to react until it is depleted andsubsequently adding more olefin monomer. When forming block copolymers,a first block of the copolymer may be formed (first homopolymericblock). Upon depletion of the first monomeric olefin, the carbon-metalbond remains stable and a second olefin monomer may be added to thereaction mixture to form a second homopolymeric block that is connectedto the first homopolymeric block. During this reaction, the second olefmmonomer first inserts into the metal-carbon bond formed between thefirst homopolymeric block and the initiator. Subsequently, the secondolefin monomer successively inserts into the metal-carbon bond formedbetween the initiator and the polymer chain of the second olefinmonomer.

As a result of the initiator's stability, polymers are formed withrelatively low polydispersities. The “polydispersity” of a polymer asused herein refers to the ratio of the weight average molecular weight(Mw) to the number average molecular weight (Mn) of the polymeraccording to equation 1. $\begin{matrix}{{POLYDISPERSITY} = \frac{\sum\limits_{i}{N_{i}M_{i}^{2}}}{\sum\limits_{i}{N_{i}M_{i}}}} & (1)\end{matrix}$

where N_(i) is the number of mer units having molecular weight M_(i).

In particular, the present invention can provide block copolymers havinglow polydispersities. Known block copolymers have been synthesized usinganionic polymerization processes, but α-olefin monomers cannot be usedin these processes. In known block copolymers, typical minimalpolydispersities are on the order of about 1.5. According to the presentinvention, block copolymers preferably have a polydispersity of at mostabout 1.4, more preferably from about 1 to about 1.3, more preferablyfrom about 1 to about 1.2, more preferably from about 1 to about 1.1,and most preferably from about 1 to 1.05. The polydispersity of apolymer can be measured directly by a variety of techniques including,for example, gel permeation chromatography or by standard tests such asthe ASTM D-1238 procedure.

It is a further advantage of the present invention that the initiator'sstability results in good block copolymer formation with minimalformation of polymers formed substantially only of individual monomericolefin units (homopolymer). That is, relatively highly pure blockcopolymer is formed. In known systems, the amount of homopolymer formedis typically about 30 wt % based on the total amount of polymer formedincluding the block copolymer. According to the present invention, theamount of homopolymer formed is at most about 25 wt % based on the totalamount of polymer formed including copolymer, more preferably at mostabout 15 wt %, and most preferably at most about 5 wt %. These puritylevels are preferably realized in combination with preferredpolydispersity levels discussed above. For example, one embodimentinvolves formation of block copolymer of polydispersity of less thanabout 1.4 with homopolymer formation of at most about 25 wt % based onthe total amount of polymer formed including copolymer.

Most known block copolymer synthesis methods are conducted attemperatures of at most about −78° C. At these low temperatures, it isdifficult to form polymers. Instead, oligomers having less than 50 merunits typically are formed. It is a further advantage of the presentinvention that living polymerization processes can be successfullyconducted at relatively high temperatures. Preferably, livingpolymerization occurs at a temperature of at least about −50° C., morepreferably at least about 0° C., most preferably at least about 25° C.At these higher temperatures in connection with the present invention,polymer blocks having at least about 50 mer units, preferably at leastabout 75 mer units, and most preferably at least about 100 mer units canbe formed.

The initiators of the present invention can be used for polymerizationof a variety of combinations of monomers to form homopolymers, randomcopolymers of any number or ratio of monomers, or block copolymers ofany number and size of blocks, while providing optionally the preferredpolydispersities and/or purities discussed above. For example, twomonomers A and B (H₂C═CHR₆ and H₂C═CHR₇) in a ratio of 2:1 can first beprovided in a reaction system, with polymerization resulting in a randomcopolymer with A and B being incorporated in a ratio of 2:1, afterdepletion of these monomers. Then, because of the stability of theinitiator, additional monomers C and D can be added to the system, andfurther polymerization will result in a product having a first block ofrandom AB and a second block of random CD. As discussed, blocks ofrelatively pure homopolymer can be provided. For example, polymerizationof A until depletion of A, followed by addition of B and polymerizationof B resulting in a block copolymer AB.

The following examples indicate certain embodiments of the presentinvention. These examples are illustrative only and should not beconstrued as limiting.

All air sensitive manipulations were conducted under a nitrogenatmosphere in a Vacuum Atmospheres drybox or under argon when usingSchlenk techniques. Pentane was washed with sulfuric/nitric acid (95/5v/v), sodium bicarbonate, and then water, stored over calcium chloride,and then distilled from sodium benzophenone ketyl under N₂. Reagentgrade diethyl ether, 1,2-dimethoxyethane, 1,4-dioxane, andtetrahydrofuran were distilled from sodium. Deuterated solvents werepassed through activated alumina and vacuum transferred to solventstorage flasks until use. Proton and carbon spectra were referencedusing the partially deuterated solvent as an internal reference.Fluorine spectra were referenced externally. Chemical shifts arereported in ppm and coupling constants are in hertz. All spectra wereacquired at about 22° C. unless otherwise noted. IR spectra wererecorded on a Perkin-Elmer FT-IR 16 spectrometer as Nujol mulls betweenKBr plates in an airtight cell. Microanalyses (C, H, N) were performedon a Perkin-Elmer PE2400 microanalyzer in our laboratory. Since theelemental analyzer measures moles of water, the %H was calculatedassuming all D present was H, but the actual molecular mass wasemployed. GPC analyses were carried out on a system equipped with twoAlltech columns (Jordi-Gell DVB mixed bed −250 mm×10 mm (i.d.)). Thesolvent was supplied at a flow rate of 1.0 mL/min. with a Knauer HPLCpump 64. HPLC grade CH₂Cl₂ was continuously dried and distilled fromCaH₂. A Wyatt Technology mini Dawn light scattering detector coupled toa Knauer differential-refractometer was employed. The differentialrefractive index increment, dn/dc, was determined assuming that allpolymer that was weighed for the run (usually about 5 mg to ±0.1 mg)eluted from the column. For poly(1-hexene) polymers, to minimize polymerweighing error the average value for dn/dc (0.049 mL/g) from 18 runs(0.045 to 0.053 mL/g) was employed and the molecular weightsrecalculated. The yields for poly(1-hexene) were essentiallyquantitative (about 97% to about 100%).

EXAMPLE 1

[NON]Ti(NMe₂)₂ was synthesized as follows. LiBu (1.6 M in hexane, 4.2mL) was added to a solution of H₂[NON] (1.09 g, 3.36 mmol) in diethylether (30 mL) at −35° C. The mixture was warmed to room temperature andstirred for 4 h. A suspension of TiCl₂(NMe₂)₂ (696 mg, 3.36 mmol) indiethyl ether (20 mL) was added to the solution containing the Li₂[NON]at −35° C. The mixture was warmed to room temperature and stirred for 15h. After filtration through Celite all volatiles were removed in vacuo.The residue was dissolved in a minimum of methylene chloride and layeredwith pentane. Cooling to −35° C. afforded orange crystalline solid;yield 864 mg (56%): ¹H NMR (C₆D₆) δ 6.92 (m, 6H), 6.63 (m, 2H), 3.13 (s,12H, NMe₂), 1.28 (s, 6H, CMe(CD₃)₂); ¹³C NMR δ (C₆D₆) 150.93, 147.12,124.37, 123.28, 120.29, 118.60, 60.20, 47.84, 32.43, 31.93(m).

EXAMPLE 2

[NON]TiCl₂ was synthesized as follows. A Schlenk tube was charged with[NON]Ti(NMe₂)₂ (379 mg, 0.83 mmol), TMSCl (270 mg, 2.49 mmol) andtoluene (10 mL). The solution was heated to 110° C. for 7 days, duringwhich time the color of the solution turned black-purple. The volatilecomponents were removed in vacuo and the residue recrystallized frommethylene chloride/pentane at −35° C.; yield 286 mg (78%): ¹H NMR (C₆D₆)δ 6.84 (m, 4H), 6.57 (m, 4H), 1.33 (s, 6H, CMe(CD₃)₂); ¹³C NMR (C₆D₆) δ147.78, 142.14, 126.71, 124.41, 120.58, 118.86, 64.77, 30.57, 30.35 (m).Anal. Calcd for C₂₀H₁₄D₁₂Cl₂N₂OTi: C, 54.43; H, 5.89; N, 6.35. Found: C,54.57; H, 5.96; N, 6.13.

EXAMPLE 3

[NON]TiMe₂ was synthesized as follows. A solution of MeMgCl in THF (3.0M, 350 μL) was added to a solution of [NON]TiCl₂ (230 mg, 0.52 mmol) inether (10 mL) at −35° C. The color immediately changed from dark purpleto orange and white solid precipitated. The mixture was warmed to roomtemperature and stirred for 15 min. All volatiles were removed in vacuoand the residue extracted with pentane (about 10 mL) over a period ofabout 5 min. The mixture was filtered through Celite and the pentaneremoved in vacuo to afford an orange red solid which was recrystallizedfrom a mixture of ether and pentane at −35° C.; yield 162 mg (78%): ¹HNMR_δ_(—)6.87 (m, 6H), 6.56 (m, 2H), 1.60 (s, 6H, TiMe₂,) 1.42 (s, 6H,CMe(CD₃)₂); ¹³C NMR (C₆D₆) δ 148.49, 143.47, 126.1, 122.05, 121.42,119.31, 64.58, 60.15, 31.37, 30.85 (m). Anal. Calcd for C₂₂H₂₀D₁₂N₂OTi:C, 65.98; H, 8.05; N, 6.99. Found: C, 66.07; H, 7.94; N, 6.84.

EXAMPLE 4

[NON]Zr(NMe₂)₂ was synthesized as follows. H₂[NON] (6.48 g, 20 mmol) andZr(NMe₂)₄ (5.34 g, 20 mmol) were dissolved in pentane (40 mL). Uponstanding at room temperature colorless crystals precipitated. After 2days the solid was filtered off (6.9 g). The supernatant wasconcentrated and cooled to −35° C. overnight yielding a second crop ofcolorless solid (1.15 g); total yield 8.05 g (80%): ¹H NMR (C₆D₆) δ 6.97(m, 6H), 6.55 (m, 2H), 2.94 (s, 12H, NMe₂), 1.33 (s, 6H, CMe(CD₃)₂); ¹³CNMR (C₆D₆) δ 147.79, 145.67, 125.62, 122.39, 118.25, 117.84, 57.04,43.60, 32.06, 31.99 (m). Anal. Calcd for C₂₄H₂₆D₁₂N₄OZr: C, 57.43; H,7.57; N, 11.16. Found: C, 57.56; H, 7.76; N, 11.16.

EXAMPLE 5

[NON]ZrI₂ was synthesized as follows. A Schlenk tube was charged with[NON]Zr(NMe₂)₂ (3.5 g, 7.0 mmol), methyl iodide (15 g, 106 mmol), andtoluene (100 mL). The pale yellow solution was heated to 50° C. for twodays, during which time white Me₄NI precipitated from the reaction andthe color of the solution turned bright orange. The Me₄NI was filteredoff, the solvents were removed from the filtrate in vacuo, and theresidue was washed with pentane (10 mL) to afford a yellow solid. Thecrude product can be recrystallized from toluene layered with pentane,but was used in subsequent reactions without further purification; yield4.14 g (89%): ¹H NMR (C₆D₆) δ 6.79 (m, 6H), 6.56 (m, 2H), 1.36 (br s,6H, CMe(CD₃)₂); ¹³C NMR (C₆D₆, 70° C.) δ 146.83, 139.43, 127.90, 123.95,123.29, 119.42, 60.21, 31.26,30.71 (m). Anal. Calcd forC₂₀H₁₄D₁₂I₂N₂OZr: C, 35.98; H, 3.93; N, 4.20. Found: C, 35.71; H, 3.94;N, 3.88.

EXAMPLE 6

[NON]ZrMe₂ was synthesized as follows. A solution of MeMgI in diethylether (2.8 M, 2.3 mL) was added to a suspension of [NON]ZrI₂ (2.119 mg,3.17 mmol) in diethyl ether (50 mL) at −35° C. The reaction mixture wasallowed to warm to room temperature and was stirred until the yellowsolid was replaced by white precipitate (30 min). All volatile solventswere then removed in vacuo and the off-white residue was extracted withpentane (50 mL). The extract was filtered and the pentane was removed invacuo. The crude product was recrystallized from a mixture of pentaneand ether to afford pale yellow crystals; yield 1.02 g (72%): ¹H NMR(C₆D₆) δ 6.90 (m, 6H), 6.53 (m, 2H), 1.36 (s, 6H, CMe(CD₃)₂), 0.84 (s,6H, ZrMe₂); ¹³C NMR (C₆D₆) δ 148.08, 142.87, 126.50, 122.46, 120.13,119.28, 57.00, 45.60, 31.13, 30.59 (m). Anal. Calcd for C₂₂H₂₀D₁₂N₂OZr:C, 59.54; H, 7.21; N, 6.31. Found: C, 59.81; H, 7.19; N, 6.39.

EXAMPLE 7

{[NON]ZrMe}[MeB(C₆F₅)₃] was synthesized as follows. A solution ofB(C₆F₅)₃ (35 mg, 67 μmol) in pentane (5 mL) that had been cooled to −35°C. was added to a solution of [NON]ZrMe₂ (30 mg, 67 μmol) in pentane (5mL). The mixture immediately turned bright yellow. A solid precipitatedwhen the B(C₆F₅)₃ solution was added at −35° C., but it dissolved whenthe mixture was warmed to room temperature. The slightly cloudy brightyellow solution was stirred at room temperature for 5 min, filtered, andcooled to −35° C. for two days. Yellow crystals were filtered off andbriefly dried in vacuo; yield 31 mg (47%): ¹H NMR (C₆D₅Br) δ 7.03-6.55(m, 8H), 2.24 (br s, 3H, BMe), 0.98 (s, 6H, CMe(CD₃)₂), 0.77 (s, 3H,ZrMe); ¹³C NMR (toluene-d₈, −30 ûC) δ 150.24, 147.16, 141.5 (m, C₆F₅),139.5 (m, C₆F₅), 137.77, 135.8 (m, C₆F₅), 123.54, 59.20, 50.90 (s,ZrMe), 29.5 (br m, ^(t)Bu, B-Me); ¹⁹F NMR (C₆D₆) δ −133.14 (d, 6F,F_(o)), −159.35 (br s, 3F, F_(p)), −164.27 (t, 6F, F_(m)).

EXAMPLE 8

{[NON]ZrMe(PhNMe₂)]}[B(C₆F₅)₄] was synthesized as follows. Solid[NON]ZrMe₂ (˜8 mg, 18 μmol) was added to a suspension of[PhNMe₂H][B(C₆F₅)₄] (15 mg, 18 μmol) in C₆D₆Br(1 mL) at −35° C. and themixture was stirred for 30 min at room temperature. ¹H NMR (C₆D₅Br) δ6.94-6.50 (m, 13H), 2.74 (s, 6H, PhNMe₂), 1.17 (s, 6H, C(CD₃)₂Me), 0.95(s, 3H, ZrMe); ¹⁹F NMR (C₆D₅Br) −131.78 (F_(o)), −162.11 (t, F_(p)),−165.94 (br m, F_(m)).

EXAMPLE 9

Ethylene was polymerized using {[NON]ZrMe}[MeB(C₆F₅)₃] as follows. Astock solution of B(C₆F₅)₃ (51 mg, 100 μmol) in toluene (5 mL) was addedto [NON]ZrMe₂ (44 mg, 100 μmol) dissolved in toluene (5 mL) at −35° C.The color changed to bright yellow. The reaction mixture was allowed towarm to room temperature. Aliquots were used for polymerizationreactions. A solution of {[NON]ZrMe}[MeB(C₆F₅)₃] in toluene (2 mL, 20μmol) was added to toluene (50 mL) and the solution was stirredvigorously under 1 atm of ethylene. White polyethylene began toprecipitate. After 120 sec the reaction was stopped by addition ofmethanol (5 mL). All solvents were removed in vacuo and the polyethylenewas washed with methanol and dried; yield 69 mg.

EXAMPLE 10

Ethylene was polymerized using {[NON]ZrMe(PhNMe₂)]}[B(C₆F₅)₄] asfollows. A stock solution of [NON]ZrMe₂ (44 mg, 100 μmol) inchlorobenzene (5 mL) was added to [PhNMe₂H][B(C₆F₅)₄] (80 mg, 100 μmol)dissolved in chlorobenzene (5 mL) at −35° C. The solution was allowed towarm to room temperature. Aliquots were employed for polymerizationreactions. A solution of {[NON]ZrMe(PhNMe₂)]}[B(C₆F₅)₄] in chlorobenzene(2 mL, 20 μmol) was added to chlorobenzene (50 mL) and the mixture wasstirred vigorously under 1 atm of ethylene. The reaction mixture becameincreasingly viscous as white polyethylene formed and precipitated.After two minutes the reaction was stopped by addition of methanol (3mL). The volume of the mixture was reduced in vacuo and the polyethylenewas precipitated by adding a large excess of methanol. The polymer wasfiltered off and dried in vacuo; yield 540 mg.

EXAMPLE 11

1-Hexene was polymerized using {[NON]ZrMe(PhNMe₂)]}[B(C₆F₅)₄] asfollows. In a typical experiment varying amounts of hexene (0.3-3.0 mL)were added to a solution of {[NON]ZrMe(PhNMe₂)]}[B(C₆F₅)₄] (about 50μmol of [PhNMe₂H][B(C₆F₅)₄] and about 1.1 equiv of [NON]ZrMe₂) inchlorobenzene at 0° C.). The carefully weighed, limiting reagent was the“activator,” [PhNMe₂H][B(C₆F₅)₄]. It is assumed that the amount ofcatalyst precursor formed is equal to the amount of activator when it isadded to a 10% excess of [NON]ZrMe₂ in chlorobenzene. ([NON]ZrMe₂ itselfis inactive.) The total volume of the reaction mixture was always 13.0mL The reaction mixture was stirred for 1.5 hour and quenched byaddition of HCl in diethyl ether (4 mL, 1.0 M). Most solvent was removedat 15 Torr (water aspirator) at 45° C.). The viscous oil was dried at100 mTorr at 50-60° C. for 20 hours. Yields and molecular weight dataare shown in Table 1. The molecular weights and polydispersities weremeasured by light scattering. The average value for dn/dc (0.049 mL/g)obtained (assuming total elution) from 18 runs (0.045 to 0.053 mL/g) wasemployed and M_(n)(found) calculated using that basis.

TABLE 1 Equiv 1-hexene μmol cat M_(n) (calcd) M_(n) (found) M_(w)/M_(n)49 49 4144 5139 1.14 179 45 15026 15360 1.08 229 52 19210 19320 1.04 28856 24262 24780 1.02 343 47 28901 24590 1.05 399 52 33592 35820 1.04 40855 34349 28030 1.03 517 43 46430 39310 1.03

EXAMPLE 12

H₂[TMSNON] synthesis was performed as follows. A solution of BuLi inhexanes (33 mL, 1.6 M) was added to a solution of O(o-C₆H₄NH₂)₂ (5.04 g,25.2 mmol) in THF (100 mL) at −35° C. The mixture was warmed up to roomtemperature and stirred for 5 h. TMSCl (7.3 mL, 58.0 mmol) was added at−35° C. The solution was warmed up to room temperature and stirred for14 h. All volatile components were removed in vacuo and the residueextracted with pentane (60 mL) over a period of about 15 min. A whitesolid was filtered off (2.4 g) and washed with pentane (20 mL). Allsolvents were removed in vacuo to give an off-white solid; yield 8.29 g(95%): ¹H NMR (C₆D₆) δ 6.88 (m, 6H), 6.59 (m, 2H), 4.22 (br s, 2H, NH),0.095 (s, 18H, SiMe₃).

EXAMPLE 13

[TMSNON]ZrCl₂ synthesis was performed as follows. H₂[TMSNON] (1.29 g,3.75 mmol) and Zr(NMe₂)₄ (1.00 g, 3.75 mmol) were dissolved in pentane(10 mL) at 25° C. After 18 hours all volatile components were removed invacuo. The off-white residue was dissolved in diethyl ether (20 mL) andTMSCl (1.4 mL, 11.25 mmol) was added. After a few minutes a solid beganto precipitate. After 90 min the volume of the mixture was reduced toabout 10 mL and pentane (20 mL) was added. Copious amounts of paleyellow powder precipitated. All solvents were removed in vacuo ; yield1.845 g (97%): ¹H NMR (C₆D₆) δ 6.78 (m, 4H), 6.54 (m, 4H), 0.25 (s, 18H,SiMe₃).

EXAMPLE 14

[TMSNON]Zr¹³Me₂ was prepared as follows. A solution of ¹³MeMgI indiethyl ether (1.4 mL, 0.9 M) was added to a suspension [TMSNON]ZrCl₂(310 mg, 0.615 mmol) in diethyl ether at −35° C. The solution was warmedup to room temperature and stirred for about 15 min during which time abrown solid precipitates. 1,4-dioxane (108 mg, 1.23 mmol) was added andall volatile components removed in vacuo. The residue was extracted withpentane (10 mL) for about 5 min. The solid was filtered off and washedwith more pentane (about 5 mL) affording a brown solid and a pale yellowfiltrate. The filtrate was evaporated to dryness and the off-whiteresidue recrystallized from a mixture of diethyl ether and pentaneaffording colorless crystalline product; yield 155 mg (54%): ¹H NMR(C₆D₆) δ 6.85 (m, 6H), 6.54 (m, 2H), 0.81 (d, J_(CH)=114 Hz, 6H,Zr¹³Me₂), 0.26 (s, 18H, SiMe₃); ¹³C NMR (C₆D₆) δ 47.16 (¹³CH₃).

EXAMPLE 15

[TMSNON]Zr¹³Me₂ was used as a polymerization initiator as follows.Inside the glove box a 100 mL flask was charged with Ph₃C[B(C₆F₅)₄] (49mg, 54 μmol) and chlorobenze (9 mL). [TMSNON]Zr¹³Me₂ (25 mg, 54 μmol)was added as a solid under stirring at −35° C. The flask was capped witha rubber septum and quickly brought outside where it was cooled to 0° C.in an ice bath. After 5 min 1-hexene (1.5 mL) was injected with a gastight syringe. After 30 min the mixture was quenched with HCl in diethylether (3 mL, 1 M). Removal of all volatile components afforded viscousmaterial; yield 860 mg (80%). Gel permeation chromatography demonstrateda polydispersity of about 1.37.

EXAMPLE 16

(2,6-i—Pr₂—C₆H₃NHCH₂CH₂)₂O was prepared as follows. Solid (TsOCH₂CH₂)₂O(5 g, 12.0 mmol) was added to a chilled solution of 2,6-i—Pr₂—C₆H₃NHLi(4.53 g, 24.8 mmol) in THF (30 ml). After stirring at RT for 24 h allvolatiles were removed in vacuo. The residue was extracted with pentane.Removal of all volatiles gave an orange oil (4.2 g, 82%) which could beused without further purification. The oil crystallized upon standing.¹H NMR (C₆D₆) δ 7.18-7.14 (br m, 6H, H_(aromat)), 3.60 (t, 2H, NH), 3.48(sep, 4H, CHMe₂), 3.35 (t, 4H, OCH₂), 3.07 (q, 4H, CH₂N), 1.06 (d, 24 H,CHMe₂).

EXAMPLE 17

[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]Zr(NMe₂)₂ was prepared as follows. A solutionof Zr(NMe₂)₄ (2.5 g, 9.4 mmol) in pentane (4 ml) was added to a solutionof (2,6-i—Pr₂—C₆H₃NHCH₂CH₂)₂O (4.0 g, 9.4 mmol) in pentane (14 ml).Almost instantaneous crystallization occurred. After standing overnightthe crystals were collected and the mother liquor was cooled to −30° C.yielding a second crop of crystals. Total yield was 3.85 g (68%). ¹H NMR(C₆D₆) δ 7.15-7.10 (br m, 6H, H_(aromat)), 3.71 (sep, 4H, CHMe₂), 3.56(t, 4H, OCH₂), 3.33 (t, 4H, CH₂N), 2.56 (s, 12H, ZrNMe₂), 1.31 (d, 12 H,CHMe₂), 1.28 (d, 12 H, CHMe₂). ¹³C NMR (C₆D₆) δ 150.2 (Ph), 146.2(o-Ph), 125.2 (p-Ph), 124.2 (m-Ph), 72.8 (OCH₂), 57.7 (CH₂N), 42.7(ZrNMe₂) 29.0 (CHMe₂), 26.9 (CHMe₂), 25.4 (CHCMe₂).

EXAMPLE 18

[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]ZrCl₂ was prepared as follows. Neat TMSCl(578 mg, 5.3 mmol) was added to a solution of[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]Zr(NMe₂)₂ (400 mg, 0.664 mmol) in 10 mldiethyl ether at RT. After thorough mixing by vigorous shaking thereaction mixture was allowed to stand overnight at RT yielding colorlesscrystals (285 mg) in 73% yield. If the ethereal solution of[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]Zr(NMe₂)₂ is too concentrated, [N₂O]Zr(NMe)Clcocrystallizes with [(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]ZrCl₂. ¹H NMR (C₆D₆) δ7.17 (br, 4H, m-Ph), 7.15 (br, 6H, p-Ph), 3.73 (sep, 4H, CHMe₂), 3.66(t, 4H, OCH₂), 3.35 (t, 4H, CH₂N), 1.51 (d, 12 H, CHMe₂), 1.26 (d, 12 H,CHMe₂). ¹³C NMR (C₆D₆) δ 146.4 (Ph), 145.1 (o-Ph), 127.6 (p-Ph), 125.1(m-Ph), 73.6 (OCH₂), 59.3 (CH₂N), 29.0 (CHMe₂), 26.9 (CHMe₂), 25.4(CHCMe₂).

EXAMPLE 19

[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]Zr(CH₂CHMe₂)₂ was prepared as follows. Achilled solution of BrMgCH₂CHMe₂ (2.51 M in ether, 286 μl, 0.72 mmol)was added to a suspension of [(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]Zr(NMe₂)₂ (205mg, 0.35 mmol) in diethyl ether (10 ml) at −30° C. A fine precipitateslowly replaced the suspension of crystals and after stirring for 1.5 hat RT dioxane (63 mg, 0.72 mmol) was added. After 20 min of additionalstirring all volatiles were removed and the residue was extracted withpentane. Recrystallization from pentane yielded 158 mg (72%) ofcolorless crystals. ¹H NMR (C₆D₆) δ 7.17-7.12 (br, 4H, H_(Ar)), 3.91(sep, 4H, CHMe₂), 3.66 (br, 8H, OCH₂CH₂N), 1.92 (m, 2H, CH₂CHMe2), 1.45(d, 12H, CHMe₂), 1.23 (d, 12H, CHMe₂), 0.85 (d, 12 H, CH₂CHMe₂), 0.70(d, 4H, CH₂CHMe₂). ¹³C NMR (C₆D₆) δ 149.2 (C_(ipso)), 146.0 (o-Ar),126.2 (p-Ar), 124.6 (m-Ar), 78.1 (CH₂CHMe₂), 74.5 (OCH₂), 58.3 (CH₂N),29.7 (CH₂CHMe₂), 28.9 (CHMe₂), 28.4 (CH₂CHMe₂), 27.4 (CHMe₂), 24.6(CHMe₂).

EXAMPLE 20

[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]ZrMe₂ was prepared as follows. A chilledsolution of BrMgMe (4.1 M in ether, 428 μl, 1.75 mol) was added to asuspension of [(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]ZrCl₂ (500 mg, 0.85 mmol) indiethyl ether (20 ml) at −30° C. A fine precipitate slowly replaced thesuspension of crystals and after stirring for 2 h at RT dioxane (154 mg,1.75 mmol) was added. After 20 min of additional stirring all volatileswere removed and the residue was extracted with pentane.Recrystallization from pentane yielded 280 mg (61%) of colorlesscrystals. ¹H NMR (C₆D₆) δ 7.15 (br, 2H, p-Ar), 7.12 (br, 4H, m-Ar), 3.84(sep, 4H, CHMe₂), 3.41 (br, 8H, OCH₂CH₂N), 1.38 (d, 12 H, CHMe₂), 1.23(d, 12 H, CHMe₂),).30 (s, 6H, ZrMe). ¹³C NMR (C₆D₆) δ 147.1 (C_(ipso)),146.5 (o-Ph), 126.5 (p-Ph), 124.7 (m-Ph), 73.6 (OCH₂), 58.6 (CH₂N), 43.6(ZrMe), 28.9 (CHMe₂), 27.3 (CHMe₂), 24.9 (CHCMe₂).

EXAMPLE 21

[NON]Hf(NMe₂)₂ was synthesized as follows. [NON]H₂ (8.964 g, 0.027 mol)and Hf(NMe₂)₄ (9.800 g, 0.027 mol) were stirred in 40 mL toluene at 115°C. in a 100 mL sealed vessel for 30 hours. Solvents were then removed invacuo and the resulting white microcrystalline solid was slurried in 20mL pentane, collected on a frit, washed with several portions ofpentane, and dried in vacuo; yield 10.141 g (62%). ¹H NMR (C₆D₆) δ 7.06(m, 2, Ar), 6.97 (m, 2, Ar), 6.90 (m, 2, Ar), 6.56 (m, 2, Ar), 3.01 (s,12, NMe₂), 1.34 (s, 6, t-Bu);

EXAMPLE 22

[NON]HfCl₂ was prepared as follows. [NON]Hf(NMe₂)₂ (961 mg, 1.631 mmol)and TMSCl (1.063 g, 9.789 mmol) were stirred in 30 mL toluene at 100° C.for 5 hours during which a yellow color developed. Solvents were removedin vacuo and the resulting yellow solid was extracted with Et₂O/toluene(30 mL/10 mL), filtered, and solvents were removed to give the productas a canary yellow microcrystalline solid; yield 657 mg (70%): ¹H NMR(C₆D₆) δ 6.80 (m, 6, Ar), 6.53 (m, 2, Ar), 1.31 (s, 6, t-Bu).

EXAMPLE 23

[NON]HfMe₂ was prepared as follows. A stirred pale yellow solution of[NON]HfCl₂ (152 mg, 0.266 mmol) in 7 mL Et₂O at −40° C. was treated withMeMgI (0.558 mmol, 2.8 M in Et₂O) whereupon MgClI precipitatedimmediately. The mixture was allowed to warm to 25° C. over 1 hour afterwhich a few drops of 1,4-dioxane were added and the mixture was stirredfor an additional 30 minutes. Solvents were removed in vacuo and theproduct was extracted from the white residue with 10 mL pentane,filtered through Celite, and the filtrate concentrated and stored at−40° C. overnight. Colorless prisms were separated from the motherliquor and dried in vacuo: yield 91 mg, (65%). ¹H NMR (C₆D₆) δ 6.94-6.83(m, 6, Ar), 6.54 (m, 2, Ar), 1.36 (s, 6, t-Bu), 0.65 (s, 6, Me)C₂₂H₂₀N₂D₁₂HfO: C, 49.76; H, 8.35 N, 5.27.

EXAMPLE 24

[NON]Hf(CH₂CH(CH₃)₂)₂ was prepared as follows. A stirred pale yellowsolution of [NON]HfCl₂ (525 mg, 0.918 mmol) in 18 mL Et₂O at −40° C. wastreated with (CH₃)₂CHCH₂MgCl (1.882 mmol, 2.5 M in Et₂O) whereupon MgCl₂precipitated immediately. The mixture was allowed to warm to 25° C. over2 hours after which a few drops of 1,4-dioxane were added and themixture was stirred for an additional 30 minutes. Solvents were removedin vacuo and the product was extracted from the white residue withpentane, filtered through Celite, and the filtrate concentrated andstored at −40° C. Large colorless prisms were separated from the motherliquor and dried in vacuo: yield 324 mg, (57%). ¹H NMR (C₆D₆) δ7.02-6.85 (m, 6, Ar), 6.56 (m, 2, Ar), 2.43 (m, 2, CH₂CHC(CH₃)₂), 1.37(s, 6, t-Bu), 1.16 (d, 12, CH₂CHC(CH₃)₂, 1.02 (d, 4, CH₂CHC(CH₃)₂,J_(HH)=6.9); ¹³C{H} NMR (C₆D₆) δ 148.29, 142.77, 126.64, 123.73, 120.18,119.48, 92.22, 31.57, 31.35, 30.81 (m, CD₃), 29.84. Anal. Calcd forC₂₈H₃₂N₂D₁₂HfO: C, 54.66; H, 9.17 N, 4.55.

EXAMPLE 25

{[NON]HfMe}[B(C₆F₅)₄]was prepared as follows. Solid [NON]HfMe₂ (15 mg,0.028 mmol) and Ph₃C[B(C₆F₅)₄] (26 mg, 0.028 mmol) were combined andthen dissolved in 0.7 mL C₆D₅Br at 25° C. to give an orange solution. ¹HNMR (C₆D₅Br) δ 7.68-6.75 (m, Ar), 2.03 (s, 3, Ph₃CMe), 1.19 (s, 6,t-Bu), 0.68 (b, 3, HfMe).

EXAMPLE 26

{[NON]HfMe(2,4-lutidine)}B(C₆F₅)₄ was prepared as follows. Solid[NON]HfMe₂ (15 mg, 0.028 mmol) and Ph₃C[B(C₆F₅)₄] (26 mg, 0.028 mmol)were combined and then dissolved in 0.7 mL C₆D₅Br in an NMR tube at 25°C. to give an orange solution. Then 2,4-lutidine (3 mg, 0.028 mmol) wassyringed into the NMR tube whereupon the solution rapidly turned yellow.¹H NMR (C₆D₅Br) δ 8.39 (b, 1, 2,4-lut), 7.29-6.66 (m, Ar), 2.21 (b, 3,Me_(ortho)), 2.03 (s, Ph₃Me), 1.96 (s, 3, Me_(para)), 1.14 (s, 6, t-Bu),0.63 (s, 3, HfMe).

EXAMPLE 27

{[NON]Hf(CH₂CHMe₂}(2,4-lutidine)}B(C₆F₅)₄ was prepared as follows. Solid[NON]Hf(CH₂CH(CH₃)₂)₂ (15 mg, 0.025 mmol) and Ph₃C[B(C₆F₅)₄] (23 mg,0.025 mmol) were dissolved in 0.7 mL C₆D₅Br at 25° C. followed bytreatment with 2,4-lutidine (3 mg, 0.025 mmol whereupon the orangesolution turned yellow. ¹H NMR (C₆D₅Br) δ 8.50 (b, 1, 2,4-lut),7.18-6.82 (m, Ar), 5.44 (s, 1, Ph₃CH), 4.68 (s, CH₂C(CH₃)₂, 2.42 (b, 4,CH₂CH(CH₃)₂) and Me_(ortho)), 2.03 (s, 3, M_(epara)), 1.61 (s,CH₂C(CH₃)₂, 1.02 (b, 6, t-Bu), 0.94 (d, 2, CH₂CH(CH₃)₂), 0.73 (d, 6,CH₂CH(CH₃)₂).

EXAMPLE 28

Polymerization of 1-hexene by {[NON]HfMe}B(C₆F₅)₄. A solution of[NON]HfMe₂ (15 mg, 0.028 mmol) and 1-hexene (24 mg, 0.28 mmol) in 0.5 mLC₆D₅Br was combined with a solution of Ph₃C[B(C₆F₅)₄] (26 mg, 0.028mmol) in 0.5 mL C₆D₅Br at −40°. The resulting orange solution wastransferred to an NMR tube. ¹H NMR after 10 minutes showed the presenceof Ph₃CMe, no 1-hexene, and several featureless broad resonances in0.8-1.70 ppm region. An additional 10 equivalents of 1-hexene (24 mg,0.28 mmol) were syringed into the NMR tube. ¹H NMR showed no remaining1-hexene.

EXAMPLE 29

Hexene was polymerized as follows. A solution of[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]Zr(CH₂CHMe₂)₂ (28 mg, 44 μmol) in PhCl (4 ml)was added to a suspention of [PhNMe₂H][B(C₆F₅)₄] (32 mg, 40 μmol) inPhCl (8 ml) at −30° and the upon warm up to room temperature for 15 min.The reaction mixture was cooled to 0° and hexene (1.0 ml, 8.0 mmol) wasadded in one shot. The reaction was quenched with HCl (1.0 M in ether, 4ml) after 80 min. All volatiles were removed in vacuo (100 mTorr) at120° C.

EXAMPLE 30

Hexene was polymerized as follows. Neat PhNMe₂ (5.1 μl, 40 μmol) and asolution of [(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]Zr(CH₂CHMe₂)₂ (28 mg, 44 μmol) inPhCl (4 ml) were subsequently added to a solution of Ph₃C[B(C₆F₅)₄] (37mg, 40 μmol) in PhCl (8 ml) at −30° and the reaction mixture was allowedto warm up to 0°. Hexene (1.0 ml, 8.0 mmol) was added in one shot andafter 80 min the reaction was quenched with HCl (1.0 M in ether, 4 ml).All volatiles were removed in vacuo (100 mTorr) at 120° C.

EXAMPLE 31

Hexene was polymerized as follows. A solution of[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]ZrMe₂ (30 mg, 55 μmol) in PhCl (3 ml) wasadded to a suspention of [PhNMe₂H][B(C₆F₅)₄] (40 mg, 50 μmol) in PhCl (9ml) at −30° and the reaction mixture stirred upon warm up to roomtemperature for 10 min. The reaction mixture was cooled to 0° and hexene(1.0 ml, 8.0 mmol) was added in one shot. The reaction was quenched withHCl (1.0 M in ether, 4 ml) after 80 min. All volatiles were removed invacuo (100 mTorr) at 120° C.

EXAMPLE 32

Hexene was polymerized as follows. A solution of[(2,6-i—Pr₂—C₆H₃NCH₂CH₂)₂O]ZrMe₂ (24 mg, 44 μmol) in PhCl (2 ml) wasadded to a suspension of [Ph₃C][B(C₆F₅)₄] (37 mg, 40 μmol) in PhCl (8ml) at −30°. The reaction mixture was mixed thoroughly by shaking andallowed to react at −30° for 5 min. Hexene (1.0 ml, 8.0 mmol) was addedin one shot and the reaction mixture was kept at −30° until the reactionwas quenched with HCl (1.0 M in ether, 4 ml) after 2 h. All volatileswere removed in vacuo (100 mTorr) at 120° C.

EXAMPLE 33

A block copolymer polyhexene and polynonene was prepared as follows.{[NON]ZrMe(PhNMe₂)}[B(C₆F₅)₄] (46 micromoles in 8.0 ml of chlorobenzene)was gene situ as described in example 11. 1-hexene (600 microliters) wasadded at 0° C. After 15 min an aliquot (1.0 ml) was taken and quenched.Addition of 1-nonene (700 microliters) to the catalystprecursor/polyhexene mixture and workup after 30 min yielded a polymer(756 mg) which showed a narrow, unimodal peak in the GPC(M_(w)/M_(n)=1.03). The molecular weight (Mn) was 23,600.

EXAMPLE 34

O[o-C₆H₄NHC(CD₃)₂CH₃]₂ (H₂[NON] was synthesized as follows.O(o-C₆H₄NH₂)₂ (18.8 g, 94 mmol) was dissolved in acetone-d₆ (120 g, 1.88mol) and activated 4 molecular sieves (30 g) were added. After thecondensation was complete (as judged by ¹H NMR) the molecular sieveswere filtered off and the unreacted ketone was removed in vacuo. Theimine dissolved in diethylether (60 mL) was slowly added to a precooledsolution (acetone/dry ice) of methyllithium in diethylether (270 mL,0.88 M). The reaction mixture was allowed to warm up to roomtemperature. After 24 h the reaction mixture was quenched by pouring itslowly into a beaker filled with 500 mL of a mixture of ice and water.The product was extracted into hexane (3×100 mL) and the combinedorganic layers were filtered through a 35 cm long and 2.5 cm widealumina column. The solvent was evaporated in vacuo to afford 16.7 g(55%) of the product as a viscous orange oil: ¹H NMR (CDCl₃) δ 7.00 (m,4H), 6.68 (m, 4H), 4.19 (br s, 2H, NH), 1.35 (s, 6H, CMe(CD₃)₂); ¹³C(CDC₃) δ 145.24, 138.34, 123.62, 117.76, 117.30, 115.96, 50.81, 29.81,29.28 (m, C(CD₃)₂Me); MS (EI) m/e 324 (M⁺). Anal. Calcd for C₂₀H₁₆D₁₂N₂O: C, 74.02; H, 8.70; N, 8.63. Found: C, 74.41; H, 8.94; N, 8.30.

Having thus described certain embodiments of the present invention,various alterations, modifications and improvements will be apparent tothose of ordinary skill in the art. Such alterations, modifications andimprovements are intended to be within the spirit and scope of thepresent invention. For example, in the aforementioned chemical species,some or all of the hydrogen atoms may be replaced with deuterium atoms.Accordingly, the foregoing description is by way of example only. Thepresent invention is limited only as defined by the following claims andthe equivalents thereto.

What is claimed is:
 1. A composition of matter comprising a structure:[R₁—X—A—Z—R₂]²⁻ wherein X and Z are each group 15 atoms, R₁ and R₂ areeach a hydrogen atom or group 14 atom-containing species and A isL₁—Y₁—L₂ wherein Y₁ is a group 16 atom, and L₁ and L₂ include at leastone group 14 atom bonded to Y₁.
 2. The composition of matter accordingto claim 1, wherein the composition of matter has a structure:


3. The composition of matter according to claim 1, wherein Y₁ is an atomselected from the group consisting of oxygen and sulfur.
 4. Thecomposition of matter according to claim 3, wherein X and Z are eachnitrogen atoms.
 5. The composition of matter according to claim 4,wherein L₁ and L₂ are bonded to X and Z respectively.
 6. The compositionof matter according to claim 3, wherein L₁ and L₂ are each C₂ units suchthat Y₁ is bonded to two carbon atoms.
 7. The composition of matteraccording to claim 3, further comprising MR₄R₅ and having a structure:

wherein M is a metal and R₄ and R₅ are each selected from the groupconsisting of halides and group 14 atom-containing species such that Xand Z each form an anionic bond to M and Y₁ forms a bond to M and thecomposition of matter has no net charge.
 8. The composition of matteraccording to claim 7, wherein M is selected from the group consisting ofTi, Zr, and Hf.
 9. The composition of matter comprising a structure:[R₁—X—A—Z—R₂]²⁻ wherein X and Z are each group 15 atoms, R₁ and R₂ areeach selected from the group consisting of hydrogen atoms, linearhydrocarbons, branched hydrocarbons and aromatic hydrocarbons and A is

wherein Y₂ is a group 15 atom, R₃ is H or a group 14 atom-containingspecies and L₁ and L₂ include at least one group 14 atom bonded to Y₂.10. The composition of matter according to claim 9, wherein X and Z areeach nitrogen atoms.
 11. The composition of matter according to claim10, wherein L₁ and L₂ are bonded to X and Z respectively.
 12. Thecomposition of matter according to claim 9, wherein L₁ and L₂ are eachC₂ units such that Y₂ is bonded to two carbon atoms.
 13. The compositionof matter according to claim 9, further comprising MR₄R₅ and having astructure:

wherein M is a metal and R₄ and R₅ are each selected from the groupconsisting of halides and group 14 atom-containing species such that Xand Z each form an anionic bond to M and Y₂ forms a bond to M and thecomposition of matter has no net charge.
 14. The composition of matteraccording to claim 13, wherein M is selected from the group consistingof Ti, Zr, and Hf.
 15. The composition of matter according to claim 10,wherein Y₂ is a nitrogen atom.
 16. The composition of matter accordingto claim 15, wherein L₁ and L₂ are bonded to X and Z, respectively. 17.The composition of matter according to claim 16, wherein L₁ and L₂ areeach C₂ units such that Y₂ is bonded to two carbon atoms.
 18. Thecomposition of matter according to claim 17, wherein R₁ and R₂ are eacharomatic hydrocarbons and R₃ is H.
 19. The composition of matteraccording to claim 17, wherein R₁ and R₂ are each linear hydrocarbonsand R₃ is H.
 20. The composition of matter according to claim 17,wherein R₁ and R₂ are each branched hydrocarbons and R₃ is H.
 21. Thecomposition of matter according to claim 17, wherein R₁ and R₂ are eacharomatic hydrocarbons and R₃ is a group 14 atom-containing species. 22.The composition of matter according to claim 17, wherein R₁ and R₂ areeach linear hydrocarbons and R₃ is a group 14 atom-containing species.23. The composition of matter according to claim 17, wherein R₁ and R₂are each branched hydrocarbons and R₃ is a group 14 atom-containingspecies.
 24. The composition of matter according to claim 17, whereinR₁, R₂ and R₃ are each H.
 25. The composition of matter according to anyone of claims 15 to 24, further comprising MR₄R₅ and having a structure:

wherein M is a metal and R₄ and R₅ are each selected from the groupconsisting of halides and group 14 atom-containing species such that Xand Z each form an anionic bond to M and Y₂ forms a dative bond to M andthe composition of matter has no net charge.
 26. The composition ofmatter according to claim 25, wherein M is selected from the groupconsisting of Ti, Zr, and Hf.